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By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors'-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By AIME AIME

IT its annual meeting on Oct. 21 and 22, the Engineers' Council for Professional Development announced the selection of J. P. H. Perry. vice-president of the Turner Construction Co. and prominent civil engineer of New York City as its new Chairman. He succeeds C. F. Scott, who becomes Chairman of its Committee on Professional Recognition. S. L. Tyler, Secretary of the American Institute of Chemical Engineers, succeeds A. B. Parsons as ECPD Secretary. R. E. Doherty is Vice-chairman. C. E. Davies remains as Assistant Secretary, as do R. L. Sackett as Chairman of the Committee on Student Selection and Guidance, O. W. Eshhach as Chairman of the Committee on Engineering Training, and Karl T. Compton as Chairman of the Committee on Engineering Schools.

Jan 1, 1938

By Richard M. Foose

FIVE miles southwest of Mt. Holly Springs, Cumberland County, Pennsylvania, the Philadelphia Clay Co. has been mining and milling a white clay since 1896; for use in white cement, as a filler in rubber, pigment and paper, in the manufacture of insecticides, and for other minor purposes. Until late in 1942, when the mine was abandoned because of labor shortage, combined underground mining and surface stripping produced approximately 30,000 tons of clay a year, of which 10,000 tons were refined in the mill. GEOLOGY Lower Cambrian Antietam quartzite and the Montalto quartzite, stratigraphically older, trend N.55°E. and make a sharp 1600-ft. anticlinal ridge of the South Mountains. The Tomstown dolomite overlies the Antietam quartzite on the southeast flank of the anticline, which is displaced near its crest by a steeply dipping oblique fault. Erosion of the less resistant Tomstown formation has resulted in a narrow valley at an elevation of 700 ft. Directly on top of the Antietam quartzite and at the base of the Tomstown formation is a zone of sandy white clay, lenticular along the strike of the formations, ranging in thickness from 10 to 300 ft. within a mile. All of the formations dip steeply to the southeast, from 65° to vertical. The clay crops out at an elevation of about 1000 feet. ORIGIN AND CHARACTER The uppermost part of the Antietam formation is sericitic and schistose at many places, and at all these places weathering is in an advanced stage. The clay is the residual product of weathering of this sericitic quartzite or sandy schist. The crude clay has the physical aspect of a sandy kaolin, but there are large areas in the clay formation that are low in free silica, and commonly the 30 ft. adjacent to the Antietam quartzite is notably free of silica. The overlying Tomstown dolomite has been weathered almost completely to a mixed yellow and brown clay, which carries a zone of nodular and chunky limonite and manganese ore, 4 to 12 ft. thick, about l00 ft. from the contact with the white clay. In mining, this zone is an important "marker," indicating where the white clay may be expected in an advancing tunnel. The contact of the white clay formation with the yellow and brown clay of the Tomstown formation is relatively sharp, although the line of contact is irregular and therefore responsible for the lenticular character of the white clay formation. Following is an analysis of the refined clay containing less than one per cent of moisture when dried at 212°F.: Si02, 67.05 per cent; A1203, 22.27; Fe203, 0.40; CaO, 0.00; Ti02, 1.05; MgO, 0.52; Na20, 0.04; K20, 0.88; ignition loss, 7.65; total, 99.86.

Jan 1, 1944

By E. B. Harden, J. H. Harden

The practical use to which topographical models or relief-maps have been put, has within the last few years taken a wider range. They are rapidly coming into favor for other than purely scientific purposes, and their value for illustration and instruction is being more fully appreciated. Topographical maps; representing by contour-curve lines the elevations and depressions of the earth's surface, are now demanded in engineering work of nearly every description, and afford a ready means of bringing out the configuration of the country in a simple manner. A beautiful example of recent topographical mapping is seen in the seventeen sheets just issued by the Geological Survey of New Jersey. By reason of the inability of unskilled persons to understand the nature of a topographical map, it is sometimes necessary to con struct the same in relief, with the rivers, canals, railroads, etc., delin eated upon it. With the aid of such a map, problems in engineer ing science which would otherwise require expert assistance to explain them, are reduced to a simple and understandable form. Relief-maps are also of value to the geologist in working out the geological structure. To the instructor they present the most ready and efficient means of imparting clear and accurate knowledge of topography and kindred subjects. To the lawyer they are invalua ble in enabling him to bring into the court-room a representation of a part of the country with all its features accurately shown, to ex plain to the court and jury the special points about which litigation is pending and which would otherwise require long and laborious description. The application of the topographical map to business purposes is shown in a relief constructed by the writers for the Cumberland Valley Railroad Company and used by that company in the various ways of calling attention to the desirability of its route. This model is based partly on actual survey and partly on sketch topography. The horizontal scale is ,%, the vertical 1/19,200 of

Jan 1, 1888

By John Norton

IN recent years, the damping capacity of metals has come to be recognized as an important index of certain types of structural change. In a number of instances, this property has proved to be particularly sensitive, but insufficient work has been done to permit a general inter-pretation. There is considerable question at the present time as to just what factors are responsible for the internal dissipation of energy when a metal is carried through a cycle of stress, and these factors must be ascertained if the value of the damping method as a metallurgical tool is to be determined. Since internal stresses are among the chief causes of dissipation of internal energy, or damping capacity, it was thought that a study of the changes in damping during the recovery and recrystalliza-tion of a cold-worked metal might throw some light upon the subject, particularly if the damping changes were correlated with other properties that are better understood. Probably more work has been done on the recrystallization phenomena of alpha brass than on any other metal, so this was chosen as the material for the present investigation. Damping measurements on brass have been made by Förster and Köster.1 They showed that the annealing of a brass that had been cold-drawn to 50 per cent reduction produced a rapid fall in the damping, a flat minimum occurring at approximately the temperature of recrystal-lization. The damping remained at a low value until grain growth was well under way and then it increased rapidly with increasing grain size. Köster and Rosenthal2 continued the work in greater detail. They pointed out that the damping decrease does not correspond to the hard-ness drop but occurs at a lower temperature, suggesting that the relief or redistribution of internal stresses has a large effect while the actual recrystallization effect is small. They also show the increase in damping at the higher annealing temperatures. Their curves are reproduced in Fig. 1.

Jan 1, 1940

By Charles Will Wright

THE economy as well as the living standards of a country depends largely upon adequate supplies of raw materials at reasonable prices. Geological and climatic conditions responsible for the occurrence of commercial minerals and the growth of raw agricultural and forest products are so varied in different parts of the world that no country can be self-sufficient. The world is rapidly shrinking because of improvement in transportation facilities, but populations are steadily increasing and so are the needs for a greater production of raw materials and for their more equitable distribution. Too many barriers between nations prevent free access to the main sources of supply of the raw materials vital to neighboring nations and it is just such barriers that are often the cause of friction and even war. The International Trade Organization is doing a commendable job in helping to. break down barriers and to reduce friction, and we should now find ways to facilitate access to these sources of supply and encourage more efficient and greater production of the raw materials so urgently needed throughout the world. This cannot be done by individual selfish governmental agencies, influenced as they are by politics, nor by socialistic governments attempting to nationalize industries. It can be done efficiently only by the free individual through private enterprise properly protected against adverse governmental action. This protection can be supplied by the World Bank.

Jan 1, 1948

EdgaR S. Cook, Pottstown, Pa.:—Many friends and acquaintances seem to be under the impression that the Warwick Iron & Steel Co. received a' license from Mr. Gayley, free of cost, as an inducement to adopt the process. This impression is not correct, since the license was paid for, and I think it was the first payment that Mr. Gayley received for the use of his process. As president of the Warwick Iron & Steel Co., I am responsible for its earnings, and with only the experience at the Isabella furnaces as a guide, the directors of the company considered that there was a great risk in expending the large sum of money required for the plant. They, however, acted favorably upon my recommendation, and to this extent I am responsible for the installation at the Warwick furnaces. I made the best agreement possible with Mr. Gayley, and naturally our company received certain advantages. It will be contrary to all experience if subsequent plants do not show some improvements and economies in construction. It is to our indirect benefit that all subsequent licenses granted by Mr. Gayley should be charged at a much higher rate than we paid; and I trust that he will see to it that all such licenses granted, especially to companies making merchant iron, shall be at a maximum figure. The Warwick Iron & Steel Go. is not interested in any way in exploiting the merits of the Gayley dry-blast process; on the contrary, looking at the subject from a narrow and selfish standpoint, it is to the advantage of our company that no merchant blast-furnace competing with our iron-product should be equipped with a dry-blast plant. There is a clause in the contract with Mr. Gayley, whereby our company agrees to furnish him with all the data derived from the operation of the dry-blast plant, and that he or his

Jan 1, 1909

By Francois E. Heuze

The Crestmore Mine of the American Cement Company lies at the eastern end of the Jurupa Mountains, 50 miles east of Los Angeles. Originally, a quarry was opened in 1908 for "limestone" used in the manufacture of cement. The mining operations eventually went underground employing first a modified system of block caving and later the "room and pillar" scheme. The limestones are relatively small roof pendants preserved in an enveloping and intrusive quartz diorite. They occur as two irregular lenticular bodies roughly parallel at the top and tending towards convergence at depth. Their dip varies between 25 and 30 degrees E. The presently mined lower bed, Chino limestone, is typically composed of alternating bands a few inches to a few feet thick of medium to coarsely granular white crystalline limestone and somewhat yellowish limestone (brucite marble). A "room and pillar" scheme of mining is currently employed in the lower body of the Crestmore Mine. The levels are horizontal and access is provided by a spiraling road starting in the old quarry. The present depth of operations is an average 750 ft below the surface. Fig. 1 gives a three-dimensional general sketch of the mine. The long axis of the rooms is in an E-W direction, normal to the strike of the beds. Fig. 2 is a horizontal map of the 130 level, the deepest level mined presently. It is in this level that most of the in-situ investigations have been conducted. The present investigation was made possible by a non-restrictive grant of the American Cement Company to the University of California. The program included a series of in-situ tests using flat-jacks, plate bearing,

Jan 1, 1968

Extremes in temperature and weather, along with the highly corrosive nature of acid leach solutions used at open-pit copper mines, necessitates the use of pipeline systems that are both corrosion resistant and impervious to the environment.

Jan 6, 1976

By M. W. Strong

The technique of handling drilling muds varies somewhat, partly because of personal factors but mainly because of differences in formation, the type of problems, and the general drilling conditions in different localities. The much greater depths to which bore holes are now carried have made necessary closer attention to and great modifications of all aspects of drilling-mud technique. Increased depth means smaller hole, smaller drill pipe, smaller clearances, higher pumping pressures, higher differential pressures between shows and the mud column, less accurate control of the weight of the mud column, delayed receipt of formation data, and poorer samples. It means longer delays and greater hazards in rectifying mistakes or dealing with accidental occurrences. Equipment on a larger scale is necessary and more pains must be taken with layout. Lastly, the budget costs of raw materials have risen to high figures and economy of time and of direct monetary expenditure have come to mean much more than formerly. A mud laboratory is now part of the essential establishment of a modern oil field and to it current problems can be submitted for the most thorough investigation. The detailed chemical properties of all materials purchased or quarried have to be investigated. Detailed data on the physical properties have to be ascertained and research on improvement of material and its most efficient use has to be carried out. In this paper will be discussed the main mud problems of Iran, some of which are peculiar to local conditions while others are of the general type common to all workers in this subject. Underground Conditions In deep wells in Iran the normal overburden may consist of: (1) up to several thousand feet of marls with interbedded sandstones and limestones of varying porosity and permeability; (2) beneath this a chemical series of rock salt and anhydrites, containing various marls and thin limestones,

Jan 1, 1939

By M. W. Strong

The technique of handling drilling muds varies somewhat, partly because of personal factors but mainly because of differences in formation, the type of problems, and the general drilling conditions in different localities. The much greater depths to which bore holes are now carried have made necessary closer attention to and great modifications of all aspects of drilling-mud technique. Increased depth means smaller hole, smaller drill pipe, smaller clearances, higher pumping pressures, higher differential pressures between shows and the mud column, less accurate control of the weight of the mud column, delayed receipt of formation data, and poorer samples. It means longer delays and greater hazards in rectifying mistakes or dealing with accidental occurrences. Equipment on a larger scale is necessary and more pains must be taken with layout. Lastly, the budget costs of raw materials have risen to high figures and economy of time and of direct monetary expenditure have come to mean much more than formerly. A mud laboratory is now part of the essential establishment of a modern oil field and to it current problems can be submitted for the most thorough investigation. The detailed chemical properties of all materials purchased or quarried have to be investigated. Detailed data on the physical properties have to be ascertained and research on improvement of material and its most efficient use has to be carried out. In this paper will be discussed the main mud problems of Iran, some of which are peculiar to local conditions while others are of the general type common to all workers in this subject. Underground Conditions In deep wells in Iran the normal overburden may consist of: (1) up to several thousand feet of marls with interbedded sandstones and limestones of varying porosity and permeability; (2) beneath this a chemical series of rock salt and anhydrites, containing various marls and thin limestones,

Jan 1, 1939

By Maurus Seet

Mainland China, with one-fourth of the world's population and one-tenth of its coal production, can no longer be ignored as a considerable force on the world energy scene. In terms of annual productivity, China's 300 million tons of coal rank third behind the Soviet Union with 655 million and the United States 557 million (1968 Minerals Yearbook. USBM). When viewed from another angle, 1967 figures show that increased productivity from all coal-producing continents, with the exception of North America, was led by Chinese-dominated Asia with a 19% gain. Not unpredictably though, China, on a per capita basis, is closer to the bottom of the list among members of the industrial community. Despite its misspent youth, and despite the set- backs caused by the Big Leap Forward of the late 50's and the Cultural Revolution of the late 60'S, the People's Republic has managed to make some impressive strides in developing its coal industry over the past twenty years.

Jan 1, 1971

By G. J. Armstrong, K. S. Lynch, C. G. Thomas, L. A. Baker, R. J. Cornelius

The presence of geothite in a hematite ore has been shown to strongly affect the time of heating to the firing temperature. The investigation of spalling of single pellets and of packed beds has enabled free water and goethite spalling to be identified as separate phenomena. In addition, it has been shown that even for an 18-in. deep bed of green balls, the free water and goethite drying periods can be considered separately. Based on this observation, a method of predicting production rate and hood temperature profile is presented. The method required knowledge of the ore goethite content, ore grind, and the green pellet bulk density. Laboratory results were found to be in good agreement with actual plant practice and have led to improved process performance.

Jan 1, 1974

Metal Statistics, Published by the American Metal Market, 111 John St , New York, N. Y. While it is not policy to list in this directory commercial publishers of literature on mining and geology, it is felt that reference to a few standard works of wide distribution and general use should be included; particularly when those works are statistical or of a specific informatory nature Metal Statistics is a book issued annually by these publishers. It contains a general assortment of statistical information concerning the ferrous and the nonferrous metals-price quotations of the metals, tables of production, and so on It is a widely used reference The 25th Annual Edition was issued in March, 1932. The price is $2

Jan 1, 1933

By F. C. Blare

THE best method for the estimation of copper in ores and secondary products is that proposed by Dr. Steinbeck* for the award offered by the Mansfeld'schen Ober-Berg-und Hutten-Direction. It is based upon the decolorization of the blue ammonia solution of copper by potassic cyanide,† It is necessary for the accurate estimation of copper in arsenides that the arsenic be separated from the copper before the ammonia solution is made. The presence of a notable amount of arsenic renders the titration by potassic cyanide inaccurate, the end reaction being obscured by the appearance of a yellowish-green tint towards the end of the titration. The change of the color of the ammonia solution from blue to the tint caused by the presence of arsenic cannot be used for an end reaction, for the intensity and quick appearance of the latter-color depend upon the amount of arsenic present in the solution. In the analysis of speise, the method of separating the copper by an oxidizing and reducing treatment in the muffle, to volatilize the arsenic, gives poor results, and there may easily be some loss of the weighed sample. The separation of the precipitated sulphides of arsenic and copper by treating with sodic sulphide, gives good results, but the process is tedious. I have used the two following methods, which are simpler and more expeditious than those mentioned, with good results. * Fresenius, Zeitschrift Air Anal. Chemie., viii, 1. †First noted by Parkes in the Mining Journal for 1861.

Jan 1, 1881

By H. J. Wasson

DEVELOPMENTS in Venezuela during the past few months have been obscured by the hap-penings in Seminole and, more recently, those in southwest Texas. The question has been asked whether or not the opening of these vast new, prolific areas in the United States may not have depressed prices to a point so low as to give the developments in the Caribbean countries a serious setback. Nothing of the kind, however, has taken place, and on the contrary, there has been demonstrated the fact that Venezuela can profitably produce great quantities of oil under existing market conditions, and at the same time finance the foundation for further large expan-sion in the future. The three big factors which contribute to place Venezuela in a unique position and tend to insure the steady expansion of its oil industry are, in the order of their importance: I. Reasonable oil laws backed by a sound govern-ment, which comprehends the all-important fact that the country's prosperity depends on the prosperity of its industries, in a word, perceiving that the goose which lays the golden egg merits considerate treatment. II. The low cost of placing Venezuela oil on our At-lantic seaboard; not over $0.60 per barrel. III. The uniformly high average production per well and the large area of some of the individual pools. Under these conditions Venezuelan producers may be expected to continue steady and profitable ex-pansion even in the face of further market slumps. Their position is analogous to that of the low-cost copper producers, and unless artificial barriers, such as tariffs, come into play, Venezuela will steadily grow in importance. Within less than five years it should be second only to the United States among the oil-producing countries of the world.

Jan 10, 1927

Map

Jan 1, 1960

By R. V. Norris

The removal of mine-water by hoisting in tanks instead of pumping, while somewhat a reversion to the methods of the ancients, has come very rapidly into favor in the anthracite region of Pennsylvania during the past few years. In fact, so much so, that at the present time there are at least eight large collieries at which all the water is hoisted, and six more plants are in preparation. The particulars of the plants in operation and under construction, as far as decided on, are given in the tables on pages 107 and 108. Besides these, the Delaware, Lackawanna and Western R.R. Co. is constructing a hoist of large capacity for a depth approximating 500 feet, to be located in the Keyser Valley, near Scranton. The hoists will be driven by electric motors, geared directly to the sheaves. The Lehigh Valley Coal Company is planning a large hoist for the Packer collieries in the Shenandoah district, but no work has been done on this as yet. The earliest regular hoisting, I believe, mas done by means of semi-cylindrical tanks (Fig. 1) at the Nanticoke collieries of the Susquehanna Coal Company. These tanks were attached under the regular shaft-carriages, taking in water through six large clack-valves in the bottom, and discharging through an endgate opened by a lever which was operated by a guide-piece on the shaft head-frame. These tanks were designed July, 1880, by the late J. H. Bowden, one of the very early members of the Institute. Similar tanks are still used in emergencies at the Nos. 1, 2, 3 and 6 shafts of the company. The objections to. their use were: that water could only be hoisted during the night-shift, or when the shafts were not in use for hoisting coal, thus requiring a very large sump, and greatly limiting the water capacity of the plants; that the alternate wetting and drying

Jan 1, 1904

By W. G. Pfann

A simple method of obtaining multistage batch separations by crystallization was described recently. Known as zone-refining, it comprises passing short molten zones through a long solid charge. This technique can now be used on a continuous basis by means of the zone-void method described in this paper. Feed enters, at an intermediate point, a column down which molten zones travel, and waste and product leave at the ends. Materials move in the column through the agency of voids, which are introduced at the ends and travel toward the feed inlet. The voids and molten zones are moved by external heaters in a simple manner, and the principle of reflux is utilized. ANEW method of obtaining multistage separations by crystallization was described recently.' Named zone-refinina.,-, the method comwrises slowly passing a series of molten zones through a long solid charge. Solute becomes concentrated at one or the other end of the charge, depending on whether it raises or lowers the freezing point of the solvent. The separation increases with the number, P, of zone-passes, approaching a limit as P approaches infinity. Zone-refining has been highly effective in purifying germanium and other substances.2,3 and new applications are steadily increasing. Zone-refining is a batch method and as such it has certain limitations inherent in batch operation. If it could be made continuous, its scope and utility would be greatly broadened. This end has been achieved by the zone-void method described in this paper. In the zone-void method feed is introduced continuously at an intermediate point in a column down which molten zones travel, while impure waste and purified product leave at the ends. Both the flows of feed, waste and product, and also the travels of the zones, are actuated by external moving heaters in a simple manner; and the system utilizes the principle of reflux. The method provides, in the field of crystallization, the counterpart of the continuous fractiona-tion column in the field of distillation. The following will be discussed: apparatus and mode of operation, fundamental nature of the separation, design theory, and practical considerations. The method will be described in terms of a binary solute-solvent system in which the solute is an impurity to be removed and the solvent is the desired product. The distribution coefficient, k, defined as the ratio of solute concentration in the solid freezing out of a molten zone to that in the liquid in the zone, is assumed to be constant and less than one. The process is equally effective for k's greater than one and for ternary or higher order systems. Method and Apparatus The essential features of a continuous zone-refining process are represented in highly generalized form in Fig. 1. A series of molten zones, produced by moving heaters, travels slowly down the column or charge (to the left in Fig. 1). If there were no flows of feed, waste, or product, the process would simply be batch zone-refining, the action of the molten zones being to sweep solute down the column, solvent up the column. For the process to be con- tinuous, with stripping and enriching sections in the column, feed must enter, and waste and product must leave, as indicated. The zone-void process accomplishes both objectives, namely, the indicated movements of zones and the indicated flows of material. Zones are moved by moving heaters, just as in batch zone-refining. Materials are made to flow by creating voids at the waste and product exits and causing these voids to move to the feed inlet. Since there must be a net flow of material from the feed inlet to each of the outlets, the indicated movements of voids are in the desired directions, because movement of a void in a given direction corresponds to flow of material in an opposite direction. In order to produce the desired movements of voids, the column is folded into two vertical sections having the feed inlet in common at their upper ends. Voids are displaced upward by the liquids in the molten zones and their travel is actuated by the motions of the zones. Voids travel with the zones in the enriching section and move continuously. Voids travel opposite to the zones in the stripping section and move intermittently. Creation and travel of voids will now be examined in detail. The enriching section of a column in operation, with its void generator, is shown in Fig. 2. The column section is a vertical tube around which a series of closely fitting, regularly spaced heaters travel slowly upward. Each heater produces a molten region, the temperatures of the heaters and the cooling between heaters being controlled so as to maintain the molten zones approximately constant in size. A void is normally present atop the molten zone in each heater. As the heater rises, it continuously melts solid above it, which drips through the void into the molten zone and continuously freezes out solid below it, of concentration k times that of the liquid in the zone. When a molten zone and void reach the feed inlet, which is kept molten, the void is displaced by an equal volume of feed liquid. Generation of voids of controlled size in the enriching section is shown in Fig. 3. The void generator is a tube of small cross-section, provided with lateral heat-conducting fins which sense the position of the heater. Liquid can escape only when the entire outlet tube is within the heater. If any part of the outlet tube is outside the heater, liquid cannot escape,

Jan 1, 1956

By H. M. St. John, T. Rynalski, G. K. Eggleston

Maintaining a satisfactory structure in brass and bronze castings has always been a foundry problem of great practical importance. While metallurgists and scientific investigators have not entirely ignored this matter, it has received less of their attention than has been given to iron, steel and the wrought copper and aluminum alloys. Investigation in this field has probably been discouraged to some extent by the complicated nature of the alloys involved. Hundreds of alloys are in more or less common use, most of them containing copper, zinc, lead and tin in widely varying proportions. They also contain appreciable percentages of iron and antimony as impurities, and often phosphorus, which has been added as a deoxidizer and fluidifier. Small amounts of sulfur are usually present. It is not uncommon to find nickel, sometimes in rather substantial quantities. Traces of other metals are frequently present. So complicated and variable a mixture obviously offers difficulties in any investigation of the various factors that influence the structure and other properties of the casting. Incipient Shrinkage Bolton and Weigandl have called attention to a type of structure characterized by intercrystalline fissures and large dendritic crystals which are frequently tarnished to an orange or reddish brown color. This intercrystalline porosity they term "incipient shrinkage" and attribute to the presence of carbon monoxide in the atmosphere under which the metal was melted. The defective structure to which Bolton and Weigand refer has become a brass-foundry problem of major importance, because it occurs with distressing frequency in leaded brasses and bronzes when these are melted in a neutral or reducing atmosphere. Since the electric furnaces, now coming into general use in brass foundries, normally operate with such an atmosphere and, in fact, depend upon it in part

Jan 1, 1930